EP0236980B1 - Verfahren zum Deodorieren von Isopropylalkohol - Google Patents

Verfahren zum Deodorieren von Isopropylalkohol Download PDF

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Publication number
EP0236980B1
EP0236980B1 EP19870103232 EP87103232A EP0236980B1 EP 0236980 B1 EP0236980 B1 EP 0236980B1 EP 19870103232 EP19870103232 EP 19870103232 EP 87103232 A EP87103232 A EP 87103232A EP 0236980 B1 EP0236980 B1 EP 0236980B1
Authority
EP
European Patent Office
Prior art keywords
resin
process according
cation exchange
palladium
exchange resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19870103232
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0236980A2 (de
EP0236980A3 (en
Inventor
Günther Osterburg
Karl-Heinz Gluzek
Wilhelm Neier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sasol Germany GmbH
Wintershall Dea International AG
Original Assignee
RWE Dea AG fuer Mineraloel und Chemie
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RWE Dea AG fuer Mineraloel und Chemie filed Critical RWE Dea AG fuer Mineraloel und Chemie
Priority to AT87103232T priority Critical patent/ATE53375T1/de
Publication of EP0236980A2 publication Critical patent/EP0236980A2/de
Publication of EP0236980A3 publication Critical patent/EP0236980A3/de
Application granted granted Critical
Publication of EP0236980B1 publication Critical patent/EP0236980B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment

Definitions

  • the invention relates to a process for the deodorization of isopropyl alcohol, which has been produced by catalytic hydration of propene, by contacting it with a fixed bed deodorization resin.
  • Isopropyl alcohol is produced in particular by reacting propene using sulfuric acid or by direct hydration on sulfonated cation exchange resins. It contains traces of various compounds that give the technical product an unpleasant smell that makes it unsuitable for further industrial processing and especially for use in the cosmetic and pharmaceutical industries.
  • the contaminants to be regarded as the cause of the smell could only be partially detected by gas chromatographic investigations.
  • Their content in technical alcohol is in the ppb range and below.
  • organic sulfur compounds such as hydrogen sulfide, carbonyl sulfide and mercaptans.
  • complex treatment processes such as distillation and adsorption processes, have been required to free the technical alcohol from these substances.
  • Deodorization by treatment with activated carbon has been carried out for many years, the activated carbon having to be regenerated at regular intervals by costly steam treatment.
  • only a few coals are suitable for such a treatment, since they either produce too much by-products, essentially acetone, are not regenerable or can only be regenerated to a limited extent or are not sufficiently effective for deodorization.
  • German Offenlegungsschrift 28 40 118 which corresponds to US Pat. No. 4,219,685
  • deodorization of C 2 and C 3 alcohols is carried out in the presence of hydrogenation-active metals, in particular nickel and platinum metals, on inorganic support materials at elevated temperature.
  • the invention is therefore based on the object of providing a deodorization process which largely removes the unpleasant smell of the technical product, is easy to handle and inexpensive and does not itself form by-products such as, in particular, ketones and ethers.
  • a neutralizingly treated, strongly acidic cation exchange resin loaded with palladium in ion form is particularly suitable for the deodorization of isopropyl alcohol which has been prepared by catalytic hydration of propene.
  • the deodorization according to the invention is carried out by passing the alcohol over the fixed bed deodorization resin at atmospheric pressure and ambient temperature. Higher pressures can be used but are not required.
  • Deodorization is generally carried out at 0 ° to 50 ° C., in particular at 10 to 30 ° C. and preferably at 15 to 25 ° C.
  • the palladium loading is preferably 0.1 to 10 g (calculated as metal) per liter of cation exchange resin and in particular 5 to 8 g (calculated as metal) per liter of cation exchange resin.
  • a complete loading of the strongly acidic cation exchange resin is sought to be acidic Avoid contact points to a large extent. These lead to side reactions, in particular to the ether formation and further condensation of acetone formed, which is undesirable.
  • the strongly acidic cation exchange resin loaded with palladium is neutralized with a mixture of alkali or alkaline earth metal hydroxide and halide in the ratio of hydroxide to halide from 85:15 to 90:10.
  • a mixture of NaOH / NaCl is used.
  • the aftertreatment with hydrohalic acid is carried out with the setting of an acid concentration of 0.01 to 0.1 n. It is especially treated with hydrochloric acid.
  • the process according to the invention is carried out in a particularly economical manner by using isopropyl alcohol which has previously been subjected to pre-deodorization on a strongly acidic cation exchange resin loaded with silver ions.
  • the strongly acidic cation exchangers used as the carrier resin are those based on synthetic resins, in particular styrene-divinylbenzene copolymers with sulfonic acid groups around an aromatic nucleus, which are also used to produce the isopropyl alcohol from propene by direct hydration. These are preferably Amberlyt @ 15 resins from Rohm & Haas. Co., USA or Lewatif s SPC 118 from Bayer AG, Leverkusen.
  • the used deodorising resin can be regenerated to recover the metal.
  • a sample is diluted with odorless water in a test tube-like glass cylinder with ground joint and glass stopper, mixed thoroughly and the smell is checked.
  • the alcohol is classified by grading several people according to the smell:
  • the final score is the sum of the points divided by the number of examiners.
  • the process according to the invention is suitable both for deodorising the dry isopropyl alcohol and for deodorising mixtures of the alcohol with water and in particular azeotropic isopropyl alcohol.
  • Palladium in the metallic form applied to inorganic carriers, can completely remove the sulfur-containing odor carriers contained in technical isopropyl alcohol.
  • the catalytic activity of the metallic palladium led to an impermissibly high conversion of isopropyl alcohol (IPA) into acetone or to a correspondingly high contamination of IPA and is therefore not suitable for the deodorization of IPA.
  • IPA isopropyl alcohol
  • the catalyst 1.2-1.4 tended to self-ignite after IPA treatment.
  • Palladium in the ionic form applied to strongly acidic cation exchangers, showed an equally good removal of the sulfur-containing odor carriers from IPA as the metallic form of palladium.
  • a catalytic converter favored by temperature and time also proved disadvantageous here Conversion of IPA, which resulted in particular from the combination of catalytically active palladium and the catalytically active acid groups of the cation exchanger to impermissible contamination of IPA by various by-products.
  • Odor The odor carriers contained in the technical IPA were completely removed. A new dull smell was noticed.
  • Permanganate time The permanganate time of the IPA had deteriorated from 35 minutes to 10 minutes (ASTM D 1363).
  • a starch acid cation exchanger Amberlyst® 15, loaded with 5.75 g Pd / I resin was prepared and treated in several equal parts with the neutralizing agents listed in Table III. Then 100 ml of resin were used to deodorize IPA. 300 ml of IPA / h were passed through in 48 hours at 20 ° C. The odor removal was good in all experiments.
  • the following table shows the acetone formation:
  • Neutral, strongly acidic cation exchangers loaded with palladium for the deodorization of IPA can also be produced by loading pre-neutralized or neutral delivery forms of commercial cation exchangers.
  • This throughput corresponds to a load of 6.6 I / I resin in each tower.
  • no analytically detectable changes in the IPA could be detected.
  • the olfactory assessment up to a runtime of 56 days showed that the odor carriers contained in the IPA used were largely removed after the first tower (odor rating 1.5-2.0), but completely (after the second tower) (odor rating 1.0) .
  • the two deodorization resins showed no deterioration in their deodorization properties even after 56 days.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP19870103232 1986-03-12 1987-03-06 Verfahren zum Deodorieren von Isopropylalkohol Expired - Lifetime EP0236980B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87103232T ATE53375T1 (de) 1986-03-12 1987-03-06 Verfahren zum deodorieren von isopropylalkohol.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3608202 1986-03-12
DE3608202A DE3608202C1 (de) 1986-03-12 1986-03-12 Verfahren zum Deodorieren von Isopropylalkohol

Publications (3)

Publication Number Publication Date
EP0236980A2 EP0236980A2 (de) 1987-09-16
EP0236980A3 EP0236980A3 (en) 1988-06-08
EP0236980B1 true EP0236980B1 (de) 1990-06-06

Family

ID=6296152

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870103232 Expired - Lifetime EP0236980B1 (de) 1986-03-12 1987-03-06 Verfahren zum Deodorieren von Isopropylalkohol

Country Status (6)

Country Link
US (1) US4709106A (enrdf_load_stackoverflow)
EP (1) EP0236980B1 (enrdf_load_stackoverflow)
JP (1) JPS62230739A (enrdf_load_stackoverflow)
AT (1) ATE53375T1 (enrdf_load_stackoverflow)
DE (2) DE3608202C1 (enrdf_load_stackoverflow)
ES (1) ES2015902B3 (enrdf_load_stackoverflow)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2628986A (en) * 1949-10-29 1953-02-17 Shell Dev Alcohol purification process
US2792344A (en) * 1953-12-14 1957-05-14 Monsanto Chemicals Methanol purification
US3373180A (en) * 1966-06-22 1968-03-12 Monsanto Co Purification process
US3433841A (en) * 1966-12-22 1969-03-18 Monsanto Co Purification process
US4219685A (en) * 1979-04-20 1980-08-26 Exxon Research & Engineering Co. Improving odor of isopropanol

Also Published As

Publication number Publication date
DE3608202C1 (de) 1987-07-02
DE3763070D1 (de) 1990-07-12
EP0236980A2 (de) 1987-09-16
EP0236980A3 (en) 1988-06-08
JPS62230739A (ja) 1987-10-09
ATE53375T1 (de) 1990-06-15
JPS6352019B2 (enrdf_load_stackoverflow) 1988-10-17
US4709106A (en) 1987-11-24
ES2015902B3 (es) 1990-09-16

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